The present invention relates to a silver halide photographic light-sensitive material containing a novel compound, more specifically, the present invention relates to a silver halide photographic light-sensitive material having high sensitivity and reduced in the residual color.
Heretofore, a great deal of efforts have been made to increase the sensitivity of silver halide photographic light-sensitive materials and reduce the persistent coloring (residual color or dye stain). Sensitizing dyes used for the spectral sensitization are known to have great effect on the capabilities of a silver halide photographic light-sensitive material. A slight difference in the structure of sensitizing dyes greatly affects the photographic capabilities such as sensitivity, fog, storage stability and residual color, however, this effect cannot be easily anticipated in advance. Therefore, many researchers have conventionally labored to synthesize a large number of sensitizing dyes and examine the photographic capabilities thereof.
The silver halide tabular grain (hereinafter referred to as a xe2x80x9ctabular grainxe2x80x9d) has the following photographic properties:
1) the ratio of the surface area to the volume is large and a large amount of a sensitizing dye can be adsorbed to the surface, so that higher spectral sensitization sensitivity can be obtained;
2) when an emulsion containing tabular grains is coated and dried, the grains orient in parallel to the support surface, so that the coated layer can be reduced in the thickness and good sharpness can be obtained;
3) the tabular grains oriented in parallel to the support maintain their shape and orientation after the development, so that the developed silver can exhibit high covering power; by virtue of this property, particularly in the case of an X-ray film, the coated silver amount necessary for obtaining an optical density of the same level as otherwise can be reduced;
4) the tabular grains oriented in parallel to the support reduce the light scattering, so that an image having high resolution can be obtained; and
5) the sensitivity to blue light is low, so that when the silver halide tabular grain is used in a green- or red-sensitive layer, a yellow filter can be reduced or dispensed with.
U.S. Pat. No. 4,439,520 describes a color photographic light-sensitive material improved in the sharpness, sensitivity and graininess by using a tabular grain having a thickness of less than 0.3 xcexcm, a diameter of 0.6 xcexcm or more and an aspect ratio of 8 or more in at least one of the green-sensitive emulsion layer and the red-sensitive emulsion layer. The aspect ratio as used herein means a ratio of the diameter of a tabular grain to the thickness. The diameter of a tabular grain as used herein means a diameter of a circle having the same area as the projected area of a grain when the emulsion is observed through a microscope or an electron microscope. The thickness as used herein is a distance between two parallel planes constituting a tabular grain.
U.S. Pat. No. 4,693,964 describes a photographic element containing silver bromide or silver iodobromide tabular grains having an average diameter of from 0.4 to 0.55 xcexcm and an aspect ratio of 8 or more, where a tabular grain having an average diameter of 0.5 xcexcm and a thickness of 0.04 xcexcm is disclosed in the Examples. U.S. Pat. No. 4,672,027 describes a photographic element containing silver bromide or silver iodobromide tabular grains having an average diameter of from 0.22 to 0.55 xcexcm and an aspect ratio of 8 or more, where a tabular grain having a thickness of 0.04 xcexcm is disclosed in the Examples.
U.S. Pat. No. 5,250,403 describes a color photographic element containing tabular grains having a (111) main plane, an average diameter of 0.7 xcexcm or more and an average thickness of less than 0.07 xcexcm in a minus blue (green and/or red) layer. Tabular grains having an average thickness of less than 0.07 xcexcm are called an xe2x80x9cultra-thinxe2x80x9d tabular grain. In this patent publication, it is stated that the ultra-thin tabular grain emulsion is advantageous in view of the relationship between the sensitivity and the graininess and that this emulsion is preferably used in a color photographic element, particularly, in a minus blue recording emulsion layer, because an image having good sharpness can be obtained.
European Patent 362699 describes a tabular grain in which the ratio of the aspect ratio to the diameter of a tabular grain is larger than 0.7, where a tabular grain having a thickness of 0.04 xcexcm is prepared in the Examples.
As such, investigations have been heretofore concentrated on the development of tabular grains having a higher aspect ratio and a smaller thickness so as to bring out the characteristic properties of the tabular grain to a higher extent. However, requirements for higher quality photographs are strong and development of techniques for achieving still higher sensitivity is keenly demanded.
As described above, the tabular grain is large in the ratio of the surface area to the volume, therefore, a large amount of a sensitizing dye can be adsorbed to the surface and thereby a higher spectral sensitization sensitivity can be obtained. Here, it is considered that by increasing the photoabsorption factor of a sensitizing dye, the efficiency in the transmission of light energy to silver halide can be increased and in turn higher spectral sensitivity can be attained.
In this way, the tabular grain is advantageous for obtaining a high spectral sensitization sensitivity but has a problem in that due to adsorption of a sensitizing dye in a large amount, the residual color after the processing increases. Thus, it is demanded to solve this problem.
From these reasons, studies are being made for a sensitizing dye having high sensitivity and reduced in the residual color.
The object of the present invention is to provide a silver halide light-sensitive material having high sensitivity and excellent storage stability and reduced in the fogging and the residual color.
As a result of extensive investigations, the object of the present invention can be attained by the following means:
(1) a silver halide photographic light-sensitive material comprising a support having provided thereon at least one emulsion layer containing silver halide grains, which comprises at least one compound represented by the following formula (I): 
wherein Z1 and Z2 each represents oxygen atom, sulfur atom, selenium atom, tellurium atom or a  greater than NR group (wherein R represents an alkyl group, an aryl group or a heterocyclic group), L1, L2 and L3 each represents a methine group, n1 represents 0, 1, 2 or 3, V1, V2, V3, V4, W1, W2, W3 and W4 each represents hydrogen atom or a substituent, provided that two substituents may be combined with each other to form a condensed ring on the condition that assuming the sum total of xcfx80 values of the substituents V1 to V4 is xcfx80v and the sum total of xcfx80 values of the substituents W1 to W4 is xcfx80w, either one of xcfx80v and xcfx80w is 0.70 or less, M represents a charge-balancing counter ion, m represents a number necessary for neutralizing the electric charge of the molecule, R1 represents an alkyl group, an aryl group or a heterocyclic group, and R2 represents a substituent represented by any of the following formulae:
xe2x80x94(La)kaCONHSO2Ra
xe2x80x94(Lb)kbSO2NHCORb
xe2x80x94(Lc)kcCONHCORc
xe2x80x83xe2x80x94(Ld)kdSO2NHSO2Rd
xe2x80x94(Le)keCOOH
wherein Ra, Rb, Rc and Rd each represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclyloxy group or an amino group, La, Lb, Lc, Ld and Le each represents a methylene group, and ka, kb, kc, kd and ke each represents an integer of 1 or more;
(2) the silver halide photographic light-sensitive material as described in (1), wherein the sum of xcfx80v and xcfx80w is 1.40 or less;
(3) the silver halide photographic light-sensitive material as described in (1) or (2), wherein either one of xcfx80v and xcfx80w is 0.70 or more and the other is 0.70 or less;
(4) the silver halide photographic light-sensitive material as described in (3), wherein xcfx80v is 0.70 or less and xcfx80w is 0.70 or more;
(5) the silver halide photographic light-sensitive material as described in (4), wherein xcfx80v is from 0.00 to 0.70 and xcfx80w is 0.70 to 1.40;
(6) the silver halide photographic light-sensitive material as described in (1), wherein the substituent R2 in the compound represented by formula (I) is xe2x80x94(Le)keCOOH;
(7) the silver halide photographic light-sensitive material as described in (6), wherein the compound represented by formula (I) is a compound represented by the following formula (II): 
wherein Z3 and Z4 each represents oxygen atom or sulfur atom, A1 represents hydrogen atom or an alkyl group, either one of V5 and W5 is a substituent selected from the group consisting of chlorine atom, bromine atom, iodine atom, a trifluoromethyl group, an ethyl group, a benzoyl group and a 1-pyrrolyl group, and the other is a substituent selected from the group consisting of hydrogen atom, fluorine atom, a methyl group, a methylthio group, an ethoxy group, an ethoxycarbonyl group, a 2-pyridyl group and a 4-pyridyl group, M1 represents a charge-balancing counter ion, m1 represents a number necessary for neutralizing the electric charge of the molecule, R3 represents an alkyl group having a sulfo group as a substituent, Lf represents a methylene group, and kf represents an integer of from 1 to 3;
(8) the silver halide photographic light-sensitive material as described in (1), wherein the substituent R2 in the compound represented by formula (I) is a substituent selected from the group consisting of xe2x80x94(La)kaCONHSO2Ra, xe2x80x94(Lb)kbSO2NHCORb, xe2x80x94(Lc)kcCONHCORc and xe2x80x94(Ld)kdSO2NHSO2Rd;
(9) the silver halide photographic light-sensitive material as described in (8), wherein the compound represented by formula (I) is a compound represented by the following formula (III): 
wherein Z5 and Z6 each represents oxygen atom or sulfur atom, A2 represents hydrogen atom or an alkyl group, V6 represents a substituent selected from the group consisting of hydrogen atom, fluorine atom, a methyl group, a methylthio group, an ethoxy group, an ethoxycarbonyl group, a 2-pyridyl group and a 4-pyridyl group, W6 represents a substituent selected from the group consisting of chlorine atom, bromine atom, iodine atom, a trifluoromethyl group, an ethyl group, a benzoyl group and a 1-pyrrolyl group, M2 represents a charge-balancing counter ion, m2 represents a number necessary for neutralizing the electric charge of the molecule, R4 represents an alkyl group having a sulfo group as a substituent, Rg represents an alkyl group, Lg represents a methylene group, and kg represents an integer of from 1 to 3; and
(10) the silver halide photographic light-sensitive material as described in (1), (2), (3), (4), (5), (6), (7), (8) or (9), wherein at least one compound represented by formula (I), (II) or (III) is contained and the emulsion layer containing the compound is formed of silver halide grains having an average aspect ratio of from 3 to 100.
The compound represented by formula (I) for use in the present invention is described in detail below.
Z1 and Z2 each represents oxygen atom, sulfur atom, selenium atom, tellurium atom or a  greater than NR group, R represents an alkyl group, an aryl group or a heterocyclic group, and R1 represents an alkyl group, an aryl group or a heterocyclic group.
Examples of the alkyl group represented by R or R1 include an unsubstituted alkyl group having from 1 to 8, preferably from 1 to 4, carbon atoms (e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl), and an alkyl group having from 1 to 8, preferably from 1 to 4, carbon atoms, which is substituted by V described below {examples of V include a halogen atom (e.g., chlorine, bromine, iodine, fluorine), a mercapto group, a cyano group, a carboxyl group, a phosphoric acid group, a sulfo group, a hydroxy group, a carbamoyl group having from 1 to 7, preferably from 2 to 5, more preferably from 2 to 3, carbon atoms (e.g., methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), a sulfamoyl group having from 0 to 7, preferably from 2 to 5, more preferably from 2 to 3 carbon atoms (e.g., methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, an alkoxy group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), an aryloxy group having from 6 to 7 carbon atoms (e.g., phenoxy, p-methylphenoxy, p-chlorophenoxy), an acyl group having from 1 to 7, preferably from 2 to 5, more preferably from 2 to 3, carbon atoms (e.g., acetyl, benzoyl, trichloroacetyl), an acyloxy group having from 1 to 7, preferably from 2 to 5, more preferably from 2 to 3, carbon atoms (e.g., acetyloxy, benzoyloxy), an acylamino group having from 1 to 7, preferably from 2 to 5, more preferably from 2 to 3, carbon atoms (e.g., acetylamino), a sulfonyl group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., methanesulfonyl, ethanesulfonyl, benzenesulfonyl), a sulfinyl group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., methanesulfinyl, benzenesulfinyl), a sulfonylamino group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino), an amino group, a substituted amino group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g,., methylamino, dimethylamino, benzylamino, anilino), an ammonium group having from 0 to 7, preferably from 0 to 5, more preferably from 0 to 3, carbon atoms (e.g., trimethylammonium, triethylammonium), a hydrazino group having from 0 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., trimethylhydrazino), a ureido group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., ureido, N,N-dimethylureido), an imido group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., succinimido), an alkyl- or aryl-thio group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., methylthio, ethylthio, carboxyethylthio, sulfobutylthio, phenylthio), an alkoxycarbonyl group having from 2 to 7, preferably from 2 to 5, more preferably from 2 to 3, carbon atoms (e.g., methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an aryloxycarbonyl group having from 6 to 7 carbon atoms (e.g., phenoxycarbonyl), an unsubstituted alkyl group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., methyl, ethyl, propyl, butyl), a substituted alkyl group having from 1 to 7, preferably from 1 to 5, more preferably from 1 to 3, carbon atoms (e.g., hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylamino-methyl; the substituted alkyl group as used herein also includes an unsaturated hydrocarbon group preferably having from 2 to 7, more preferably from 2 to 5, still more preferably from 2 to 3, carbon atoms (e.g., vinyl, ethynyl, 1-cyclohexenyl, benzylidine, benzylidene)), a substituted or unsubstituted aryl group having from 6 to 7 carbon atoms (e.g., phenyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl) and a heterocyclic group having from 1 to 7, preferably from 2 to 5, carbon atoms (e.g., pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl); two of these substituents may be combined with each other to have a structure where a benzene ring, a naphthalene ring, an anthracene ring or a heterocyclic ring is condensed; these substituents each may be further substituted by V thereon}.
Examples of the aryl group represented by R or R1 include an unsubstituted aryl group having from 6 to 20, preferably from 6 to 10, more preferably from 6 to 8, carbon atoms (e.g., phenyl, 1-naphthyl), and a substituted aryl group having from 6 to 20, preferably from 6 to 10, more preferably from 6 to 8, carbon atoms (e. g., the above-described aryl group substituted by V, specifically, p-methoxyphenyl group, p-methylphenyl, p-chlorophenyl).
Examples of the heterocyclic group represented by R or R1 include an unsubstituted heterocyclic group having from 1 to 20, preferably from 3 to 10, more preferably from 4 to 8, carbon atoms (e.g., 2-furyl, 2-thienyl, 2-pyridyl, 3-pyrazolyl, 3-isooxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2-(1,3,5-triazolyl), 3-(1,2,4-triazolyl), 5-tetrazolyl), and a substituted heterocyclic group having from 1 to 20, preferably from 3 to 10, more preferably from 4 to 8, carbon atoms (e.g., the above-described heterocyclic group substituted by V, specifically, 5-methyl-2-thienyl, 4-methoxy-2-pyridyl).
R is preferably an alkyl group, more preferably a substituted or unsubstituted alkyl group having from 1 to 6 carbon atoms, still more preferably an unsubstituted alkyl group having from 1 to 4 carbon atoms.
Z1 and Z2 each is preferably oxygen atom or sulfur atom, and at least one of Z1 and Z2 is more preferably sulfur atom.
R1 is preferably an alkyl group, more preferably an alkyl group having an acidic group (for example, a sulfo group, a carboxyl group, a sulfato group, a phosphono group, a borono group or a substituent described above for R2), still more preferably an alkyl group having from 1 to 6 carbon atoms and having a sulfo group, particularly preferably a sulfoalkyl group having from 2 to 4 carbon atoms.
The methine group represented by L1, L2 or L3 may be unsubstituted or substituted and when substituted, examples of the substituent are the same as those of the substituent V.
n1 is 0, 1 or 2 and when n1 is 2, two pairs of L2 and L3 may be the same or different. Also, two methine groups may be combined with each other to form a ring.
In a preferred embodiment of the compound, n1 is 1, L1 and L3 each is an unsubstituted methine group, and L2 is a methine group substituted by an alkyl group. The alkyl group on the methine group represented by L2 is preferably a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, more preferably methyl or ethyl.
V1, V2, V3, V4, W1, W2, W3 and W4 each represents hydrogen atom or a substituent and two of these substituents may be combined with each other to form a condensed ring.
The xcfx80 value used in the present invention is described below. The xcfx80 value is a parameter showing the effect of a substituent upon the hydrophilicity/hydrophobicity of a molecule of a compound and is defined by the following formula:
xcfx80=logP(PhX)xe2x88x92logP(PhH)
wherein P is a distribution coefficient of the compound to octanol/water and the difference between the logP value of substituted benzene PhX and the logP value of benzene is assigned to the xcfx80 value of the substituent X. The logP value can be determined based on the actual measurement according to the method described in the following publication (a) or can be determined by the calculation using the fragment method described in the publication (a) or the software package described in the publication (b). In the case where the found value does not agree with the calculated value, the found xcfx80 value is used in principle.
(a) C. Hansch and A. J. Leo, Substituent Constants for Correlation Analysis in Chemistry and Biology, John Wiley and Sons, New York (1979)
(b) Medichem software package (Ver. 3.54) developed by and available from Pomona College, Claremont, Calif.
Incidentally, for example, when V1 and V2 are combined with each other to form a naphthazole ring system, the xcfx80 value assigned to V1 and V2 can be determined as follows by regarding the xe2x80x94CHxe2x95x90CHxe2x80x94CHxe2x95x90CHxe2x80x94 as a substituent. The same applies to other condensed rings.
xcfx80(xe2x80x94(CH)4xe2x80x94)=logP(naphthalene)xe2x88x92logP(benzene)=1.32 
The xcfx80 values of respective substituents determined as above are listed in the publication (a). Main substituents are selected and their xcfx80 values are shown below.
In the present invention, assuming that the total sum of the xcfx80 values of the substituents V1 to V4 is xcfx80v and the total sum of the xcfx80 values of the substituents W1 to W4 is xcfx80w, either one of xcfx80v and xcfx80w must be 0.70 or less. The sum of xcfx80v and xcfx80w is preferably 1.40 or less. Furthermore, it is preferred that either one of xcfx80v and xcfx80w is 0.70 or more and the other is 0.70 or less, more preferably one is from 0.70 to 1.40 and the other is from 0.00 to 0.70, still more preferably xcfx80v is 0.70 or less and xcfx80w is 0.70 or more, and most preferably xcfx80v is from 0.00 to 0.70 and xcfx80w is from 0.70 to 1.40.
Ra, Rb, Rc and Rd in the group represented by R2 each represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclyloxy group or an amino group. Preferred examples thereof are described below.
Preferred examples thereof include an unsubstituted alkyl group having from 1 to 18, preferably from 1 to 10, more preferably from 1 to 5, carbon atoms (e.g., methyl, ethyl, propyl, butyl), a substituted alkyl group having from 1 to 18, preferably from 1 to 10, more preferably from 1 to 5, carbon atoms (e.g., hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl; the substituted alkyl group as used herein also includes an unsaturated hydrocarbon group preferably having from 2 to 18, more preferably from 3 to 10, still more preferably from 3 to 5, carbon atoms (e.g., vinyl, ethynyl, 1-cyclohexenyl, benzylidine, benzylidene)), a substituted or unsubstituted aryl group having from 6 to 20, preferably from 6 to 15, more preferably from 6 to 10, carbon atoms (e.g., phenyl, 1-naphthyl, p-carboxyphenyl, p-nitrophenyl, 3,5-dichlorophenyl, p-cyanophenyl, m-fluorophenyl, p-tolyl), a heterocyclic group having from 1 to 20, preferably from 2 to 10, more preferably from 4 to 6, carbon atoms (e.g., pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydrofurfuryl), an alkoxy group having from 1 to 10, preferably from 1 to 8, carbon atoms (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-hydroxyethoxy, 2-phenylethoxy), an aryloxy group having from 6 to 20, preferably from 6 to 12, more preferably from 6 to 10, carbon atoms (e.g., phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy), a heterocyclyloxy group having from 1 to 20, preferably from 3 to 12, more preferably from 3 to 10, carbon atoms (e.g., 2-thienyloxy, 2-morpholinooxy), and an amino group having from 0 to 20, preferably from 0 to 12, more preferably from 0 to 8, carbon group (e.g., amino, methylamino, dimethylamino, ethylamino, diethylamino, hydroxyethylamino, benzylamino, anilino, diphenylamino, morpholino formed into a ring, pyrrolidino). These groups each may be substituted by the substituent V.
Among these, more preferred are methyl, ethyl and hydroxyethyl, still more preferred is methyl.
The methylene group represented by La, Lb, Lc, Ld or Le may be unsubstituted or substituted by a substituent and the substituent is not particularly limited but preferred examples thereof include the substituent V.
Specific examples of the substituted methylene group include a methyl-substituted methylene group, an ethyl-substituted methylene group, a phenyl-substituted methylene group, a hydroxy-substituted methylene group and a halogen (e.g., chlorine, bromine)-substituted methylene group. The methylene group is preferably an unsubstituted methylene group.
ka, kb, kc, kd and ke each represents an integer of 1 or more, preferably from 1 to 4, more preferably 1 or 2, still more preferably 1. When ka, kb, kc, kd and ke each is 2 or more, the repeated La, Lb, Lc, Ld or Le may not be the same.
The dissociative groups NH and OH of R2 are denoted by the non-dissociative form in all cases but these can take a dissociated form (Nxe2x88x92 or Oxe2x88x92) . Actually, these groups assume the dissociated state or the non-dissociated state depending on the environment where the dye is present, such as pH.
With respect to the notation, the group in the dissociated state is denoted, for example, as Nxe2x88x92. In the case where a cationic compound (for example, sodium ion) is present as a counter salt, the notation is Nxe2x88x92Na+. Even in the non-dissociated state, if the cationic compound as a counter salt is regarded as a proton, the notation of Nxe2x88x92H+ may be used.
Preferred examples of R2 are shown below. In all cases, the dissociative group is denoted by the non-dissociated form.
R2a=xe2x80x94CH2CONHSO2CH3
R2b=xe2x80x94CH2COOH
R2c=xe2x80x94CH2SO2NHCOCH3
R2d=xe2x80x94CH2CONHCOCH3
R2e=xe2x80x94CH2SO2NHSO2CH3
xe2x80x83R2f=xe2x80x94(CH2)2CONHSO2CH3
R2g=xe2x80x94(CH2)2COOH
R2h=xe2x80x94(CH2)2SO2NHCOCH3
R2i=xe2x80x94(CH2)2CONHCOCH3
R2j=xe2x80x94(CH2)2SO2NHSO2CH3
In the above, the groups positioned earlier are more preferred. Among these, particularly preferred are R2a and R2b .
M is contained in the formula so as to show the presence of cation or anion when such ion is necessary for neutralizing the ion charge. Whether a dye is cation or anion or whether or not a dye has a net ion, depends on the substituent. Typical examples of the cation include inorganic cation such as hydrogen ion, alkali metal ion (e.g., sodium ion, potassium ion, lithium ion), alkaline earth metal ion (e.g., calcium ion) and an organic anion such as ammonium ion (e.g., ammonium ion, tetraalkylammonium ion, pyridinium ion, ethylpyridinium ion). The anion may be either inorganic anion or organic anion and examples thereof include halide anion (e.g., fluoride anion, chloride anion, bromide ion, iodide ion), substituted arylsulfonate ion (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (e.g., 1,3-benzenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (e.g., methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion and trifluoromethanesulfonate ion.
Among those cations, preferred are sodium ion, potassium ion, triethylammonium ion, tetraethylammonium ion, pyridinium, ethylpyridinium ion and methylpyridinium ion. Among those anions, preferred are perchlorate ion, iodide ion, bromide ion and substituted arylsulfonate ion (e.g., p-toluenesulfonate ion).
m represents a number of 0 or more necessary for balancing the electric charge in the molecule and when an inner salt is formed, m is 0. m is preferably a number of from 0 to 4.
The compound represented by formula (I) is more preferably a compound represented by formula (II) or (III).
The compound represented by formula (II) is described in detail below.
Z3 and Z4 each represents oxygen atom or sulfur atom. Preferably, at least one of Z3 and Z4 is sulfur atom and more preferably, both are sulfur atom.
A1 represents hydrogen atom or an alkyl group and preferred examples of the alkyl group include the unsubstituted or substituted alkyl groups described above for R. The alkyl group is more preferably a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, still more preferably methyl or ethyl.
Either one of V5 and W5 is a substituent selected from the group consisting of hydrogen atom, fluorine atom, a methyl group, a methylthio group, an ethoxy group, an ethoxycarbonyl group, a 2-pyridyl group and a 4-pyridyl group, preferably hydrogen atom or fluorine atom. The other is a substituent selected from the group consisting of chlorine atom, bromine atom, iodine atom, a trifluoromethyl group, an ethyl group, a benzoyl group and a 1-pyrrolyl group, preferably chlorine atom or bromine atom.
The alkyl group having a sulfo group as a substituent, represented by R3, may have a substituent other than the sulfo group. For example, oxygen or other non-carbon atomic group may be interposed between the sulfo group and the alkyl group as in a sulfopropyloxyethyl group. The alkyl group is preferably an alkyl group directly substituted by a sulfo group, more preferably a 3-sulfopropyl group, a 3-sulfobutyl group or a 4-sulfobutyl group.
Preferred examples of the methylene group represented by Lf are the same as those described above for La. The methylene group is more preferably an unsubstituted methylene group.
kf is an integer of from 1 to 3, preferably 1 or 2, more preferably 1.
The compound represented by formula (III) is described in detail below.
Z5 and Z6 each represents oxygen atom or sulfur atom. Preferably, at least one Z5 and Z6 is sulfur atom, and more preferably, both are sulfur atom.
A2 represents hydrogen atom or an alkyl group and preferred examples of the alkyl group include those described above as preferred examples of the unsubstituted or substituted alkyl group represented by R. The alkyl group is more preferably a substituted or unsubstituted alkyl group having from 1 to 4 carbon atoms, still more preferably methyl or ethyl.
V6 is a substituent selected from the group consisting of hydrogen atom, fluorine atom, a mercapto group, a methyl group, a methylthio group, an ethoxy group, an ethoxycarbonyl group, a 2-pyridyl group and a 4-pyridyl group, preferably hydrogen atom or fluorine atom, more preferably fluorine atom.
W6 is a substituent selected from the group consisting of chlorine atom, bromine atom, iodine atom, a trifluoromethyl group, an ethyl group, a benzoyl group and a 1-pyrrolyl group, preferably chlorine atom or bromine atom, more preferably chlorine atom.
R4 represents an alkyl group having a sulfo group as a substituent and preferred examples thereof are the same as those described above for R3. The alkyl group is more preferably an alkyl group directly substituted by a sulfo group, still more preferably a 3-sulfopropyl group, a 3-sulfobutyl group or a 4-sulfobutyl group.
Preferred examples of the alkyl group represented by Rg are the same as those described above for Ra and the alkyl group is more preferably methyl or ethyl, still more preferably methyl.
Preferred examples of the methylene group represented by Lg are the same as those described above for La and the methylene group is more preferably an unsubstituted methylene group.
kg is an integer of from 1 to 3, preferably 1 or 2, more preferably 1.
Specific examples of the compounds represented by formulae (I), (II) and (III) of the present invention are shown below, however, the present invention is by no means limited thereto. 
The compounds represented by formulae (I), (II) and (III) of the present invention can be synthesized according to the methods described in the following publications:
a) F. M. Harmer, Heterocyclic Compounds-Cyanine dyes and related compounds, John Wiley and Sons, New York, London (1964);
b) D. M. Sturmer, Heterocyclic Compounds-Special topics in heterocyclic chemistry, Chap. 8, Sec. 4, pp. 482-515, John Wiley and Sons, New York, London (1977); and
c) Rodd""s Chemistry of Carbon Compounds, 2nd ver. Vol. 4, part B, Chap. 15, pp. 369-422, Elsevier Science Publishing Company Inc., New York (1977).
(Synthesis of Compound II-1)
To 50 ml of methanol, 4.81 g of 4-{2-(2-ethoxy-1-butenyl)-5-chloro-3-benzothiazolio}butanesulfonate and 2.88 g of 3-carboxymethyl-2-methylbenzothiazolium bromide were added. The resulting solution was stirred at room temperature and thereto 8.5 ml of triethylamine was added dropwise, whereupon the solution immediately turned into a violet solution. This solution was stirred at room temperature for 3 hours, then filtered and after adding thereto 20 ml of acetic acid and further adding 250 ml of ethyl acetate, stirred under ice cooling, as a result, crystals precipitated. The crystals were filtered and then washed with methanol and subsequently with acetone to obtain 4.30 g of crude crystals of Compound II-1. The crude crystals were dissolved in 80 ml of methanol and 3 ml of triethylamine and after adding thereto 5 ml of acetic acid, heated and then concentrated by distilling off the solvent. As a result, crystals precipitated. Thereafter, this solution was cooled with ice and the crystals were filtered, washed and dried to obtain 3.85 g of Compound II-1 (yield: 68%).
xcexmax (MeOH)=548.7 nm
(Synthesis of Compound III-1)
To 50 ml of methanol, 4.65 g of 4-{2-(2-ethoxy-1-butenyl)-5-fluoro-3-benzothiazolio}butanesulfonate and 4.00 g of 5-chloro-3-methanesulfonylcarbamoylmethyl-2-methylenzothiazolium bromide were added. The resulting solution was stirred at room temperature and thereto 8.5 ml of triethylamine was added dropwise, whereupon the solution immediately turned into a violet solution This solution was stirred at room temperature for 3 hours, then filtered and after adding thereto 17 ml of acetic acid, stirred under ice cooling, as a result, crystals precipitated. The crystals were filtered and then washed with methanol and subsequently with acetone to obtain 4.50 g of crude crystals of Compound III-1. The crude crystals were dissolved in 80 ml of methanol and 3 ml of triethylamine and after adding thereto 5 ml of acetic acid, heated and then concentrated by distilling off the solvent. As a result, crystals precipitated. Thereafter, this solution was cooled with ice and the crystals were filtered, washed and dried to obtain 3-99 g of Compound III-1 (yield: 60%).
xcexmax (MeOH)=551.4 nm
The compound represented by formula (I), (II) or (III) of the present invention may be incorporated into the silver halide emulsion of the present invention by directly dissolving the compound in the emulsion or may be added to the emulsion after dissolving the compound in a solvent such as water, methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propano1, 3-methoxy-1-butanol, 1-methoxy-2-propanol or N,N-dimethylformamide, or a mixed solvent thereof.
Other than these, the compound may be incorporated by the method of dissolving a dye in a volatile organic solvent, dispersing the solution in water or hydrophilic colloid, and adding the dispersion into an emulsion described in U.S. Pat. No. 3,469,987, the method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding the dispersion to an emulsion described in JP-B-46-24185 (the term xe2x80x9cJP-Bxe2x80x9d as used herein means an xe2x80x9cexamined Japanese patent publicationxe2x80x9d), the method of dissolving a dye in an acid and adding the resulting solution to an emulsion, or forming an aqueous solution while allowing an acid or base to be present together and then adding the aqueous solution to an emulsion described in JP-B-44-23389, JP-B-44-27555 and JP-B-57-22091, the method of forming an aqueous solution or colloid dispersion while allowing a surfactant to be present together and adding it to an emulsion described in U.S. Pat. Nos. 3,822,135 and 4,006,026, the method of dispersing a dye directly in a hydrophilic colloid and adding the resulting dispersion to an emulsion described in JP-A-53-102733 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published Japanese patent applicationxe2x80x9d) and JP-A-58-105141, or the method of dissolving a dye using a compound capable of red shifting, and adding the resulting solution to an emulsion described in JP-A-51-74624. For the dissolution, an ultrasonic wave may also be used.
The compound represented by formula (I), (II) or (III) of the present invention may be added to the silver halide emulsion of the present invention in any step during the preparation of the emulsion, which is heretofore recognized as useful. The addition may be performed at any time or step as long as it is before the coating of the emulsion, for example, during the formation of silver halide grains and/or before the desalting, during the desalting and/or after the desalting but before the initiation of chemical ripening as disclosed in U.S. Pat. Nos. 2,735,766, 3,628,960, 4,183,756 and 4,225,666, JP-A-58-184142 and JP-A-60-196749, immediately before or during the chemical ripening, or after the chemical ripening but before the coating as disclosed in JP-A-58-113920. Also, as disclosed in U.S. Pat. 4,225,666 and JP-A-58-7629, the same compound solely or in combination with a compound having a different structure may be added in parts, for example, during the grain formation and during or after the completion of chemical ripening, or before- or during the chemical ripening and after the completion of chemical ripening. When added in parts, the -kind of the compound or the combination of compounds may be varied.
The added amount of the compound represented by formula (I), (II) or (III) of the present invention varies depending on the shape and size of silver halide grain, however, it is usually from 1xc3x97106 to 1xc3x9710xe2x88x922 mol, preferably from 2xc3x9710xe2x88x926 to 8xc3x9710xe2x88x923 mol, more preferably from 6xc3x9710xe2x88x926 to 6xc3x9710xe2x88x923, per mol of silver halide. The compound of the present invention may be used alone but is preferably used in combination with other spectral sensitizing dye.
The silver halide photographic light-sensitive material of the present invention is descried in detail below.
The silver halide which can be used in the silver halide photographic light-sensitive martial of the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. Among these, preferred are silver bromide, silver iodobromide, silver chlorobromide iodochlorobromide and silver halide having high silver chloride content described in JP-A-2-42, more preferred are silver bromide and silver iodobromide.
The silver halide grain contained in the photographic emulsion may be a grain having a regular crystal form such as cubic, octahedral or tetradecahedral form, a grain having an irregular crystal form such as spherical or tabular form, or a mixture thereof. In the present invention, the emulsion suitably contains grains having the above-described regular crystal form in a proportion of 50% or more, preferably 70% or more, more preferably 90% or more.
The emulsion preferably comprises tabular grains having an aspect ratio of 3 or more, more preferably from 8 to 100.
The emulsion for use in the present invention can be prepared by the method described, for example, in P. Glafkides, Chemie et Phisique Photographique, Paul Montel (1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), and V. L. Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press (1964). More specifically, any of an acidic process, a neutral process and an ammonia process may be used, and the reaction form between a soluble silver salt and a soluble halogen salt may be any of a single jet method, a double jet method and a combination thereof. Also, the grain can be formed in an atmosphere of excess silver ion (so-called reverse mixing method) . As one mode of the double jet method, a so-called controlled double jet method where the pAg of a liquid phase in which the silver halide is formed is kept constant, may also be used. According to this method, the silver halide emulsion obtained can have a regular crystal form and a nearly uniform grain size.
The silver halide emulsion for use in the present invention is usually subjected to chemical sensitization and spectral sensitization. For the chemical sensitization, chemical sensitization using a chalcogen sensitizer (to speak specifically, sulfur sensitization represented by the addition of a labile sulfur compound, selenium sensitization by a selenium compound, and tellurium sensitization by a tellurium compound) , noble metal sensitization represented by gold sensitization, and reduction sensitization may be used individually or in combination. Preferred examples of the compound for use in the chemical sensitization include those described in JP-A-62-215272, from page 18, right lower column to page 22, right upper column.
The silver halide emulsion for use in the present invention may contain various compounds or precursors thereof, for the purpose of preventing the fogging during the production, storage or photographic processing of a light-sensitive material or stabilizing the photographic capabilities. Specific preferred examples of such compounds include those described in JP-A-62-215272, pp. 39-72. Also, 5-arylamino-1,2,3,4-thiatriazole compounds (the aryl residue has at least one -electron withdrawing group) described in EP-A-447647 may be preferably used.
With respect to various techniques and inorganic/organic materials which can be used in the silver halide photographic light-sensitive material of the present invention, those described in Research Disclosure, Nos. 308119 (1989) and 37038 (1995) may be generally used.
In addition, to speak more specifically, the technique and inorganic/organic material which can be used in color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied, are described in the following portions of EP-A-436938 and cited patents therein.
The silver halide emulsion prepared according to the present invention can be used for both color photographic light-sensitive material and black-and-white light-sensitive material. Examples of the color photographic light-sensitive material include color paper, color photographing film and color reversal film, and examples of the black-and-white photographic light-sensitive material include X-ray film, general photographing film and printing light-sensitive material film. Among these, preferred is color reversal film.
The present invention can be preferably applied to silver halide color photographic light-sensitive materials having a transparent magnetic recording layer. The silver halide light-sensitive material having a magnetic recording may be prepared in such a manner that a previously heat-treated polyester thin layer support described in detail in JP-A-6-35118, JP-A-6-17528 and JIII Journal of Technical Disclosure No. 94-6023 (for example, a polyethylene aromatic dicarboxylate-base polyester support), having a thickness of from 50 to 300 xcexcm, preferably from 50 to 200 xcexcm, more preferably from 80 to 115 xcexcm, is heat treated (annealed) at a temperature of from 40xc2x0 C. to a glass transition temperature for 1 to 1,500 hours, the support is then subjected to a surface treatment such as ultraviolet irradiation described in JP-B-43-2603, JP-B-43-2604 and JP-B-45-3828, corona discharge described in JP-B-48-5043 and JP-A-51-131576, and glow discharge described in JP-B-35-7578 and JP-B-46-43480, undercoating described in U.S. Pat. 5,326,689 is applied thereon, a subbing layer described in U.S. Pat. No. 2,761,791 is provided, if desired, and ferromagnetic particles described in JP-A-59-23505, JP-A-4-195726 and JP-A-6-59357 are coated thereon.
The magnetic layer may be coated like stripes as described in JP-A-4-124642 and JP-A-4-124645.
The support may further be subjected to an antistatic treatment described in JP-A-4-62543, if desired, and finally, a silver halide photographic emulsion is coated thereon. For the silver halide grain used here, those described in JP-A-4-166932, JP-A-3-41436 and JP-A-3-41437 may be used.
This silver halide photographic light-sensitive material is preferably manufactured according to a manufacture control method described in JP-B-4-86817 and the manufacturing data are preferably recorded thereon by the method described in JP-B-6-87146. After or before the recording, the light-sensitive material is cut into a film smaller in the width than conventional 135 size films, and two perforations are punched in one side per one small-format picture according to the method described in JP-A-4-125560 so as to match the format picture smaller than conventional films.
The thus-prepared film is loaded in a cartridge package described in JP-A-4-157459, a cartridge described in JP-A-5-210202, FIG. 9, a film patrone described in U.S. Pat. No. 4,221,479 or a cartridge described in U.S. Pat. Nos. 4,834,306, 4,834,366, 5,226,613 and 4,846,418, and then used.
The film cartridge or film patrone used here is preferably of such a type that the tongue can be housed as described in U.S. Pat. Nos. 4,848,693 and 5,317,355 in view of the light-shielding property.
Also, a cartridge having a lock mechanism described in U.S. Pat. No. 5,296,886, a cartridge capable of indicating the use state described in U.S. Pat. No. 5,347,334 or a cartridge having a function of preventing double exposure is preferably used.
Furthermore, a cartridge where the film can be easily loaded by merely inserting the film into the cartridge described in JP-A-6-85128 may also be used.
The thus-produced film cartridge may be used for various photographic enjoyments by performing the photographing and development processing to satisfy the object using a camera, a developing machine or a laboratory machine.
The film cartridge (patrone) can fully exert its function when, for example, a camera in a simple loading system described in JP-A-6-8886 and JP-A-6-99908, a camera having an automatic winding-up system described in JP-A-6-57398 and JP-A-6-101135, a camera where the film can be taken out and exchanged on the way of photographing described in JP-A-6-205690, a camera where the photographing information such as panorama photographing, high-vision photographing or normal photographing (capable of magnetic recording such that the print aspect ratio can be selected) can be magnetic recorded on the film described in JP-A-5-293138 and JP-A-5-283382, a camera having a function of preventing double exposure described in JP-A-6-101194 or a camera having a function to indicate the use state of the film or the like described JP-A-5-150577, is used.
The thus-photographed film may be processed in an automatic developing machine described in JP-A-6-222514 and JP-A-6-212545 and before, during or after the processing, the use method of magnetic recording on a film described in JP-A-6-95265 and JP-A-4-123054 may be used. Also, the print aspect ratio selecting function described in JP-A-5-19364 may be used.
At the time of development processing of the film, in the case of cine-type development, the film is spliced according to the method described in JP-A-5-119461 before the processing.
During or after the development processing, the film may be subjected to an attaching/detaching operation described in JP-A-6-148805.
After such processing, the film information may be converted into a print through back printing or front printing on a color paper according to the method described in JP-A-2-184835, JP-A-4-186335 and JP-A-6-79968.
Furthermore, the film may be returned to the user together with the index print and the cartridge for return described in JP-A-5-11353 and JP-A-5-232594.